NO20170132A1 - Microbiocidal preparation - Google Patents

Microbiocidal preparation Download PDF

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NO20170132A1
NO20170132A1 NO20170132A NO20170132A NO20170132A1 NO 20170132 A1 NO20170132 A1 NO 20170132A1 NO 20170132 A NO20170132 A NO 20170132A NO 20170132 A NO20170132 A NO 20170132A NO 20170132 A1 NO20170132 A1 NO 20170132A1
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microbiocidal
preparation
microbiocides
ppm
microorganisms
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NO20170132A
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NO340977B1 (en
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John William Ashmore
Kiran Pareek
Beat Heer
Beverly Jean El A'mma
Richard Levy
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Rohm & Haas
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/02Acyclic compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02Amines; Quaternary ammonium compounds
    • A01N33/04Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02Amines; Quaternary ammonium compounds
    • A01N33/12Quaternary ammonium compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/12Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46N-acyl derivatives
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44Guanidine; Derivatives thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • A01N59/20Copper
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00Drugs for disorders of the alimentary tract or the digestive system

Abstract

Synergistic microbicidal compositions containing N-methyl-1,2-benzisothiazolin-3-one.

Description

Den foreliggende oppfinnelse vedrører en synergistisk kombinasjon av utvalgte mikrobiocider med større aktivitet enn det som ville bli iakttatt for de individuelle mikrobiocider. The present invention relates to a synergistic combination of selected microbiocides with greater activity than would be observed for the individual microbiocides.

I noen tilfeller kan kommersielle mikrobiocider ikke frembringe effektiv kontroll med mikroorganismer, selv i høye konsentrasjoner, på grunn av svak aktivitet mot visse typer mikroorganismer, for eksempel de som er resistente mot noen mikrobiocider, eller på grunn av aggressive miljøforhold. Kombinasjoner av forskjellige mikrobiocider anvendes noen ganger for å frembringe total kontroll med mikroorganismer i et spesielt sluttanvendelsesmiljø. For eksempel beskrives det i amerikansk patent-søknad 2007/00078118 synergistiske kombinasjoner av N-metyl-1,2-benzisotiazolin-3-on (MBIT) med andre biocider. Imidlertid er der et behov for ytterligere kombinasjoner av mikrobiocider som har økt aktivitet mot forskjellige stammer av mikroorganismer for å frembringe effektiv kontroll med mikroorganismene. Videre er der et behov for kombinasjoner som inneholder lavere nivåer av de individuelle mikrobiocider for miljømessig og økonomisk nytte. Problemet den foreliggende oppfinnelse befatter seg med er å frembringe slike ytterligere kombinasjoner av mikrobiocider. In some cases, commercial microbiocides cannot produce effective control of microorganisms, even at high concentrations, due to weak activity against certain types of microorganisms, such as those resistant to some microbiocides, or due to aggressive environmental conditions. Combinations of different microbiocides are sometimes used to produce total control of microorganisms in a particular end-use environment. For example, US patent application 2007/00078118 describes synergistic combinations of N-methyl-1,2-benzisothiazolin-3-one (MBIT) with other biocides. However, there is a need for additional combinations of microbiocides that have increased activity against different strains of microorganisms to produce effective control of the microorganisms. Furthermore, there is a need for combinations that contain lower levels of the individual microbiocides for environmental and economic benefit. The problem with which the present invention is concerned is to produce such additional combinations of microbiocides.

Oppfinnelsen vedrører et mikrobiocidisk preparat som omfatter (a) N-metyl-1,2-benzisotiazolin-3-on og (b) propylenglykolkaprylat. The invention relates to a microbiocidal preparation comprising (a) N-methyl-1,2-benzisothiazolin-3-one and (b) propylene glycol caprylate.

Slik de benyttes her har de følgende termer de angitte definisjoner med mindre sammenhengen klart angir noe annet. "MBIT" er N-metyl-1,2-benzisotiazolin-3-on. Termen "mikrobiocid" henviser til en forbindelse som er i stand til å drepe, inhibere veksten av eller holde veksten av mikroorganismer under kontroll på et locus. Mikrobiocider omfatter baktericider, fungicider og algicider. Termen "mikro-organisme" omfatter for eksempel sopp (så som gjær og mugg), bakterier og alger. Termen "locus" henviser til et industrielt system eller produkt som er utsatt for forurensning av mikroorganismer. Følgende forkortelser benyttes i beskrivelsen: ppm = deler per million etter vekt (vekt/vekt), ATCC = American Type Culture Collection, MBC = minste biocidiske konsentrasjon, og MIC = minste hemmende konsentrasjon. Med mindre annet er angitt er temperaturer i °C, og henvisninger til prosenter (%) er etter vekt. Mengder organiske mikrobiocider er gitt på basis av en aktiv bestanddel i ppm (vekt/vekt). As used here, the following terms have the given definitions unless the context clearly indicates otherwise. "MBIT" is N-methyl-1,2-benzisothiazolin-3-one. The term "microbiocide" refers to a compound capable of killing, inhibiting the growth of, or keeping the growth of microorganisms under control at a locus. Microbiocides include bactericides, fungicides and algicides. The term "microorganism" includes, for example, fungi (such as yeast and mold), bacteria and algae. The term "locus" refers to an industrial system or product that is subject to contamination by microorganisms. The following abbreviations are used in the description: ppm = parts per million by weight (w/w), ATCC = American Type Culture Collection, MBC = minimum biocidal concentration, and MIC = minimum inhibitory concentration. Unless otherwise stated, temperatures are in °C, and references to percentages (%) are by weight. Amounts of organic microbiocides are given on the basis of an active ingredient in ppm (w/w).

Preparatene ifølge oppfinnelsen har uventet vist seg å frembringe økt mikrobiocidisk effektivitet i et nivå av kombinerte aktive bestanddeler som er lavere enn nivået for de individuelle mikrobiocider. Ytterligere mikrobiocider utover de som er opplistet i kravene kan foreligge i preparatet. The preparations according to the invention have unexpectedly been shown to produce increased microbiocidal efficiency at a level of combined active ingredients that is lower than the level of the individual microbiocides. Additional microbiocides beyond those listed in the requirements may be present in the preparation.

I en utførelsesform av oppfinnelsen inneholder det mikrobiocidiske preparat N-metyl-1,2-benzisotiazolin-3-on og propylenglykolkaprylat. Fortrinnsvis er et vektforhold propylenglykolkaprylat og N-metyl-1,2-benzisotiazolin-3-on fra 1:0,442 til 1:0,0018. In one embodiment of the invention, the microbiocidal preparation contains N-methyl-1,2-benzisothiazolin-3-one and propylene glycol caprylate. Preferably, a weight ratio of propylene glycol caprylate to N-methyl-1,2-benzisothiazolin-3-one is from 1:0.442 to 1:0.0018.

Mikrobiocidene i preparatet ifølge oppfinnelsen kan anvendes "som de er" eller kan først formuleres med et løsemiddel eller en fast bærer. Egnete løsemidler omfatter for eksempel vann; glykoler, så som etylenglykol, propylenglykol, dietylenglykol, dipropylenglykol, polyetylenglykol og polypropylenglykol; glykoletere; alkoholer, så som metanol, etanol, propanol, fenetylalkohol og fenoksypropanol; ketoner, så som aceton og metyletylketon; estere, så som etylacetat, butylacetat, triacetylsitrat, og glyseroltriacetat; karbonater, så som propylenkarbonat og dimetylkarbonat; samt blandinger av disse. Det foretrekkes at løsemidlet velges fra vann, glykoler, glykoletere, estere og blandinger av disse. Egnete faste bærere omfatter for eksempel cyklodekstrin, silikaer, diatoméjord, vokser, cellulosematerialer, alkali- og jordalkali (for eksempel natrium, magnesium, kalium) metallsalter (for eksempel klorid, nitrat, bromid, sulfat) samt trekull. The microbiocides in the preparation according to the invention can be used "as is" or can first be formulated with a solvent or a solid carrier. Suitable solvents include, for example, water; glycols, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol; glycol ethers; alcohols, such as methanol, ethanol, propanol, phenethyl alcohol and phenoxypropanol; ketones, such as acetone and methyl ethyl ketone; esters, such as ethyl acetate, butyl acetate, triacetyl citrate, and glycerol triacetate; carbonates, such as propylene carbonate and dimethyl carbonate; as well as mixtures of these. It is preferred that the solvent is selected from water, glycols, glycol ethers, esters and mixtures thereof. Suitable solid carriers include, for example, cyclodextrin, silicas, diatomaceous earth, waxes, cellulosic materials, alkali and alkaline earth (for example sodium, magnesium, potassium) metal salts (for example chloride, nitrate, bromide, sulphate) and charcoal.

Når en mikrobiocidbestanddel formuleres i et løsemiddel kan formuleringen eventuelt inneholde overflateaktive stoffer. Når slike formuleringer inneholder overflateaktive stoffer er de generelt i form av emulsive konsentrater, emulsjoner, mikroemulsive konsentrater eller mikroemulsjoner. Emulsive konsentrater danner emulsjoner ved tilsetning av en tilstrekkelig mengde vann. Mikroemulsive konsentrater danner emulsjoner ved tilsetning av en tilstrekkelig mengde vann. Slike emulsive og mikro emulsive konsentrater er generelt velkjente på området. Det foretrekkes at slike formuleringer er uten overflateaktive stoffer. US patentskrift. 5.444.078 kan konsul-teres for ytterligere generelle og spesifikke detaljer om fremstillingen av forskjellige mikroemulsjoner og mikroemulsive konsentrater. When a microbiocidal ingredient is formulated in a solvent, the formulation may optionally contain surfactants. When such formulations contain surfactants, they are generally in the form of emulsive concentrates, emulsions, microemulsive concentrates or microemulsions. Emulsifying concentrates form emulsions by adding a sufficient amount of water. Microemulsive concentrates form emulsions by adding a sufficient amount of water. Such emulsive and micro emulsive concentrates are generally well known in the field. It is preferred that such formulations are without surfactants. US patent document. 5,444,078 can be consulted for further general and specific details on the preparation of various microemulsions and microemulsive concentrates.

En mikrobiocidbestanddel kan også formuleres i form av en dispersjon. Løsemiddel-bestanddelen i dispersjonen kan være et organisk løsemiddel eller vann, fortrinnsvis vann. Slike dispersjoner kan inneholde hjelpestoffer, for eksempel koløsemidler, fortykningsmidler, frosthindrende midler, dispergeringsmidler, fyllstoffer, pigmenter, overflateaktive stoffer, biodispergeringsmidler, sulfosuccinater, terpener, furanoner, polykationer, stabilisatorer, avsetningsinhibitorer og antikorrosjonstilsetningsmidler. A microbiocidal component can also be formulated in the form of a dispersion. The solvent component in the dispersion can be an organic solvent or water, preferably water. Such dispersions may contain auxiliaries, for example coal solvents, thickeners, antifreeze agents, dispersants, fillers, pigments, surfactants, biodispersants, sulfosuccinates, terpenes, furanones, polycations, stabilizers, deposit inhibitors and anti-corrosion additives.

Når hver av de to mikrobiocider først formuleres med et løsemiddel, kan løse-middelet som anvendes for det første mikrobiocid være det samme som eller forskjellig fra løsemiddelet som anvendes til å formulere det andre kommersielle mikrobiocid, selv om vann foretrekkes for de fleste industrielle biocidanvendelser. Det foretrekkes at de to løsemidler er blandbare. When each of the two microbiocides is first formulated with a solvent, the solvent used for the first microbiocide may be the same as or different from the solvent used to formulate the second commercial microbiocide, although water is preferred for most industrial biocide applications. It is preferred that the two solvents are miscible.

Fagfolk på området vil forstå at mikrobiocidbestanddelene ifølge den foreliggende oppfinnelse kan tilsettes til et locus i rekkefølge, samtidig eller kan blandes før de tilsettes til locuset. Det foretrekkes at den første mikrobiocid- og den andre mikrobiocidbestanddel tilsettes til et locus samtidig eller i rekkefølge. Når mikrobiocidene tilsettes samtidig eller i rekkefølge kan hver individuell bestanddel inneholde hjelpestoffer, så som for eksempel løsemiddel, fortykningsmidler, frosthindrende midler, fargestoffer, chelatdannere (så som etylendiamin- tetraeddiksyre, etylendiamindirav-syre, iminodiravsyre og salter av disse), dispergeringsmidler, overflateaktive stoffer, biodispergeringsmidler, sulfosuccinater, terpener, furanoner, polykationer, stabilisatorer, avsetningsinhibitorer og korrosjonshemmende tilsetningsmidler. Those skilled in the art will understand that the microbiocidal ingredients of the present invention can be added to a locus in sequence, simultaneously or can be mixed before they are added to the locus. It is preferred that the first microbiocidal and the second microbiocidal component are added to a locus simultaneously or sequentially. When the microbiocides are added simultaneously or in sequence, each individual component may contain auxiliaries, such as, for example, solvents, thickeners, antifreeze agents, dyes, chelating agents (such as ethylenediamine tetraacetic acid, ethylenediaminediacetic acid, iminodisuric acid and salts thereof), dispersants, surfactants , biodispersants, sulfosuccinates, terpenes, furanones, polycations, stabilizers, deposit inhibitors and corrosion-inhibiting additives.

De mikrobiocidiske preparater ifølge oppfinnelsen kan anvendes til å inhibere veksten av mikroorganismer eller høyere former for liv i vann (så som protozoer, invertebrater, bryozoer, dinoflagellater, kreps, bløtdyr etc) ved innføring av en mikrobiocidisk effektiv mengde av preparatene på, inn i eller ved et locus som er utsatt for mikrobeangrep. Egnete loci omfatter for eksempel industrielt prosessvann; avleiringssystemer for elektroovertrekk; kjøletårn; luftvaskere, gassvaskere; mineral-oppslemminger; avløpsvannbehandling; prydfontener; omvendt osmosefiltrering; ultrafiltrering; ballastvann; fordampningskondensatorer; varmevekslere; væsker og tilsetningsmidlerfor masse- og papirbearbeidelse; stivelse; plast; emulsjoner; dispersjoner; malinger; latekser; belegg, så som lakker; bygningsprodukter, så som mastiks, fugemasse og tetningsmasse; bygningsklebemidler, så som keramiske klebemidler, teppebaksideklebemidler og laminerende klebemidler; industri- eller forbrukerklebemidler; fotografiske kjemikalier; trykkvæsker; husholdningsprodukter, så som rengjøringsmidler for baderom og kjøkken; kosmetika; toalettartikler; sjampoer; såper; syntetiske vaskemidler; industrirengjøringsmidler; gulvpoleringsmidler; meieriskyllevann; metallbearbeidelsesvæsker; transportbåndsmøremidler; hydrauliske væsker; lær og lærprodukter; tekstiler; tekstilprodukter; trevirke og treprodukter, så som finér; sponplate, veggplate, flakplate, laminerte bjelker, orientert fiberplate, hard fiberplate samt partikkelplate; petroleumbearbeidelsesvæsker; drivstoff; oljefeltvæsker, så som injeksjonsvann, fraksjonsvæsker og boreslam; hjelpestoffer for jordbrukskonservering; konservering av overflateaktive stoffer; medisinsk utstyr; konservering av diagnosereagenser; matvarekonservering, så som matinnpakningsmaterialer av plast eller papp; prosesspasteuriseringsapparaterfor matvarer, drikkevarer og industriprodukter; toalettstoler; rekreasjonsvann, svømme-bassenger og velværesentre. The microbiocidal preparations according to the invention can be used to inhibit the growth of microorganisms or higher forms of life in water (such as protozoa, invertebrates, bryozoans, dinoflagellates, crayfish, molluscs, etc.) by introducing a microbiocidally effective amount of the preparations onto, into or at a locus that is susceptible to microbial attack. Suitable loci include, for example, industrial process water; deposition systems for electrocoating; cooling tower; air scrubbers, gas scrubbers; mineral slurries; wastewater treatment; ornamental fountains; reverse osmosis filtration; ultrafiltration; ballast water; evaporative condensers; heat exchangers; liquids and additives for pulp and paper processing; starch; plastic; emulsions; dispersions; paints; latexes; coatings, such as varnishes; building products, such as mastics, sealants and sealants; building adhesives, such as ceramic adhesives, carpet backing adhesives and laminating adhesives; industrial or consumer adhesives; photographic chemicals; pressure fluids; household products, such as bathroom and kitchen cleaners; cosmetics; toiletries; shampoos; soaps; synthetic detergents; industrial cleaning agents; floor polishes; dairy rinse water; metalworking fluids; conveyor belt lubricants; hydraulic fluids; leather and leather products; textiles; textile products; wood and wood products, such as veneer; chipboard, wallboard, flakeboard, laminated beams, oriented strand board, hard fiberboard and particleboard; petroleum processing fluids; fuel; oilfield fluids, such as water for injection, fracturing fluids and drilling muds; auxiliaries for agricultural conservation; preservation of surfactants; medical equipment; preservation of diagnostic reagents; food preservation, such as plastic or cardboard food wrapping materials; process pasteurizers for foodstuffs, beverages and industrial products; toilet seats; recreational waters, swimming pools and wellness centers.

Fortrinnsvis anvendes de mikrobiocidiske preparater ifølge oppfinnelsen til å inhibere veksten av mikroorganismer i et locus valgt fra én eller flere av mineraloppslem-minger, bearbeidelsesvæsker og tilsetningsmidlerfor tremasse og papir; stivelse; emulsjoner; dispersjoner; malinger; latekser; belegg; bygningsklebemidler, så som keramiske klebemidler, klebemidler for teppebaksider; fotografiske kjemikalier; trykkvæsker; husholdningsprodukter, så som rengjøringsmidler for baderom og kjøkken; kosmetika, toalettartikler; sjampoer, såper; syntetiske vaskemidler; industri-rengjøringsmidler; gulvpoleringsmidler; meieriskyllevann; metallbearbeidelsesvæsker; tekstilprodukter; trevirke og treprodukter; konservering av hjelpestoffer for jordbruk; konservering av overflateaktive stoffer; diagnosereagenskonservering; matvarekonservering samt prosesspasteuriseringsapparater for matvarer, drikkevarer og industriprodukter. Preferably, the microbiocidal preparations according to the invention are used to inhibit the growth of microorganisms in a locus selected from one or more of mineral slurries, processing fluids and additives for wood pulp and paper; starch; emulsions; dispersions; paints; latexes; coating; building adhesives, such as ceramic adhesives, carpet backing adhesives; photographic chemicals; pressure fluids; household products, such as bathroom and kitchen cleaners; cosmetics, toiletries; shampoos, soaps; synthetic detergents; industrial cleaning agents; floor polishes; dairy rinse water; metalworking fluids; textile products; wood and wood products; preservation of auxiliaries for agriculture; preservation of surfactants; diagnostic reagent preservation; food preservation as well as process pasteurization devices for food, beverages and industrial products.

Den spesifikke mengde av preparatet ifølge oppfinnelsen som er nødvendig for å inhibere eller holde veksten av mikroorganismer og høyere livsformer i vann under kontroll i et locus avhenger av det spesielle locus som skal beskyttes. Typisk er mengden av preparatet ifølge oppfinnelsen for å holde veksten av mikroorganismer i et locus under kontroll tilstrekkelig dersom den frembringer fra 0,1 til 1,000 ppm av isotiazolinbestanddelen i preparatet i locuset. The specific amount of the preparation according to the invention which is necessary to inhibit or keep the growth of microorganisms and higher life forms in water under control in a locus depends on the particular locus to be protected. Typically, the amount of the preparation according to the invention to keep the growth of microorganisms in a locus under control is sufficient if it produces from 0.1 to 1,000 ppm of the isothiazoline component in the preparation in the locus.

Det foretrekkes at isotiazolinbestanddelene i preparatet foreligger i locuset i en It is preferred that the isothiazoline components in the preparation are present in the locus in a

mengde på minst 0,5 ppm, mer foretrukket minst 4 ppm og mest foretrukket minst 10 ppm. Det foretrekkes at isotiazolinbestanddelene i preparatet foreligger i locuset i en mengde på ikke mer enn 1000 ppm, mer foretrukket ikke mer enn 500 ppm og mest foretrukket ikke mer enn 200 ppm. amount of at least 0.5 ppm, more preferably at least 4 ppm and most preferably at least 10 ppm. It is preferred that the isothiazoline components in the preparation are present in the locus in an amount of no more than 1000 ppm, more preferably no more than 500 ppm and most preferably no more than 200 ppm.

EKSEMPLER. EXAMPLES.

Materialer og metoder. Materials and methods.

Synergismen til kombinasjonen ifølge oppfinnelsen ble demonstrert ved testing av et bredt område av konsentrasjoner av og forhold mellom forbindelsene. The synergism of the combination according to the invention was demonstrated by testing a wide range of concentrations of and ratios of the compounds.

Ett mål på synergisme er den industrielt aksepterte metode som er beskrevet av, F.C.Kull, P.C. Eisman; H.D Sylwestrowicz og R.L Mayer i "Applied Microbiology", Vol 9, 1961, p 538-541 ved anvendelse av forholdet som er bestemt av formelen One measure of synergism is the industrially accepted method described by, F.C.Kull, P.C. Iceman; H.D Sylwestrowicz and R.L Mayer in "Applied Microbiology", Vol 9, 1961, p 538-541 using the ratio determined by the formula

hvor: where:

Qa= konsentrasjon av forbindelse A (første bestanddel) i ppm, når den virker alene, som frembrakte et endepunkt (MIC av forbindelse A). Qa= concentration of compound A (first component) in ppm, when acting alone, which produced an endpoint (MIC of compound A).

Qa= konsentrasjon av forbindelse A i ppm, i blandingen, som frembrakte et endepunkt. Qa= concentration of compound A in ppm, in the mixture, which produced an endpoint.

Qb= konsentrasjon av forbindelse B (andre bestanddel) i ppm, når den virker alene, som frembrakte et endepunkt (MIC av forbindelse B). Qb= concentration of compound B (second component) in ppm, when acting alone, which produced an endpoint (MIC of compound B).

Qb= konsentrasjon av forbindelse B i ppm, i blandingen, som frembrakte et endepunkt. Qb= concentration of compound B in ppm, in the mixture, which produced an endpoint.

Når summen av Q3/Qaog Qt/Q-B er større enn én indikeres antagonisme. Når summen er lik én indikeres additivitet, og når den er mindre enn én demonstreres synergisme. Jo lavere Sl er desto større er synergien som vises av den spesielle blanding. Den minste hemmende konsentrasjon (MIC) av et mikrobiocid er den minste konsentrasjon som ble testet under et spesifikt sett av betingelser som hindrer veksten av tilsatte mikroorganismer. When the sum of Q3/Qa and Qt/Q-B is greater than one, antagonism is indicated. When the sum is equal to one, additivity is indicated, and when it is less than one, synergism is demonstrated. The lower Sl is, the greater the synergy shown by the particular mixture. The minimum inhibitory concentration (MIC) of a microbiocide is the smallest concentration tested under a specific set of conditions that prevents the growth of added microorganisms.

Synergitester ble utført under anvendelse av standard mikrotiterplateprøver med medier utformet for optimal vekst av testmikroorganismen. Minimalt saltmedium supplert med 0,2 % glukose og 0,1 % gjærekstrakt (M9GY medium) ble anvendt for testing av bakterier. Potetdekstrosebuljong (PDB medium) ble anvendt for testing av gjær og mugg. I denne metode ble et bredt område av kombinasjoner av mikrobiocider testet ved å gjennomføre MIC- prøver med høy oppløsning i nærvær av forskjellige konsentrasjoner av MBIT. MIC- prøver med høy oppløsning ble bestemt ved tilsetning av varierende mengder mikrobiocid til én søyle av en mikrotiter plate og utførelse av etterfølgende tifoldige fortynninger ved anvendelse av et automatisert væskebehandlingssystem for å oppnå en serie endepunkter som strakk seg fra 2 ppm til 10 000 ppm aktiv bestanddel. Synergy tests were performed using standard microtiter plate samples with media designed for optimal growth of the test microorganism. Minimal salt medium supplemented with 0.2% glucose and 0.1% yeast extract (M9GY medium) was used for testing bacteria. Potato dextrose broth (PDB medium) was used for yeast and mold testing. In this method, a wide range of combinations of microbiocides were tested by performing high resolution MIC assays in the presence of different concentrations of MBIT. High-resolution MIC samples were determined by adding varying amounts of microbiocide to one column of a microtiter plate and performing subsequent tenfold dilutions using an automated liquid processing system to achieve a series of endpoints ranging from 2 ppm to 10,000 ppm active constituent.

Synergien til kombinasjonene ifølge oppfinnelsen ble bestemt mot atskillige mikroorganismer, slik som beskrevet i tabellene nedenfor. Bakteriene ble anvendt i en konsentrasjon på ca 5 x 10<6>bakterier per ml og gjæren og muggen i 5 x 10<5>sopper per ml. Disse mikroorganismer er representative for naturlige forurensninger i mange forbruker- og industrianvendelser. Platene ble visuelt evaluert for mikrobevekst (turbiditet) for å bestemme MIC etter forskjellige inkubasjonstider ved 25 °C (gjær og mugg) eller 30 °C (bakterier). The synergy of the combinations according to the invention was determined against several microorganisms, as described in the tables below. The bacteria were used in a concentration of approximately 5 x 10<6> bacteria per ml and the yeast and mold in 5 x 10<5> fungi per ml. These microorganisms are representative of natural contaminants in many consumer and industrial applications. The plates were visually evaluated for microbial growth (turbidity) to determine the MIC after different incubation times at 25 °C (yeasts and molds) or 30 °C (bacteria).

Testresultatene for demonstrasjon av synergi av MBIT kombinasjonene ifølge oppfinnelsen er vist nedenfor i tabellene 1 -8. I hver test var den andre bestanddel (B) MBIT, og den første bestanddel (A) var det andre, kommersielle mikrobiocid. Hver tabell viser de spesifikke kombinasjoner av MBIT og den annen bestanddel, resultater mot de testede mikroorganismer med inkubasjonstider, endepunktaktivitet i ppm målt med MIC for MBIT alene (QB), for den annen bestanddel alene (QA), for MBIT i blandingen (Qb) og for den annen bestanddel i blandingen (Qa), den beregnete Sl- verdi, samt området for synergistiske forhold for hver testet kombinasjon (annen bestanddel/M BIT eller A/B). The test results for demonstration of synergy of the MBIT combinations according to the invention are shown below in tables 1-8. In each test, the second component (B) was MBIT, and the first component (A) was the other commercial microbiocide. Each table shows the specific combinations of MBIT and the second component, results against the tested microorganisms with incubation times, endpoint activity in ppm measured by MIC for MBIT alone (QB), for the second component alone (QA), for MBIT in the mixture (Qb) and for the other component in the mixture (Qa), the calculated Sl value, as well as the range of synergistic conditions for each tested combination (other component/M BIT or A/B).

Claims (2)

1. Mikrobiocidisk preparat,karakterisert vedat det inneholder: (a) N-metyl-1,2-benzisotiazolin-3-on, og (b) propylenglykolkaprylat.1. Microbiocidal preparation, characterized in that it contains: (a) N-methyl-1,2-benzisothiazolin-3-one, and (b) propylene glycol caprylate. 2. Mikrobiocidisk preparat i samsvar med krav 1,karakterisert vedat vektforholdet mellom propylenglykolkaprylat og N-metyl-1,2-benzisotiazolin-3-on er fra 1:0,442 til 1:0,0018.2. Microbiocidal preparation in accordance with claim 1, characterized in that the weight ratio between propylene glycol caprylate and N-methyl-1,2-benzisothiazolin-3-one is from 1:0.442 to 1:0.0018.
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